Background technology
Fluoroplastics have excellent material behavior, and as corrosion-resistant in high-and low-temperature resistance, electrical insulating property is good, and non-binding property etc. is applied to the high-tech military fields such as Aeronautics and Astronautics the earliest.More and more extensive along with its purposes also used in a large number in the various piece of automobile.Because fluoroplastics have the superior performance of operating condition of anti-particular surroundings the and low frictional properties, self-lubricating property, present a kind of polytetrafluoroethylene (PTFE) sleeve pipe has been used for the cable lining pipe of car gear shifting system, make gear shift comfortable more flexibly, replaced gradually the internal lining pipe of the materials such as traditional high density polyethylene(HDPE) (HDPE), polypropylene (PP), polyoxymethylene (POM), polybutylene terephthalate (PBT).But have due to polytetrafluoroethylene (PTFE) itself under the effect of stress, it can produce molecule segment from the deadly defect of creep, be that abrasion resistance properties is low, in use constantly rub with drag-line, make fluoroplastic sleeve internal surface damage by friction and delamination, after the automobilism certain hour, reduce its gear shift comfortable function flexibly, reduced work-ing life.
existing technique means is to fill the inorganic material powder material, glass fibre or inorganic materials coordinate with organic materials to fill improves the polytetrafluoroethylene (PTFE) creep resistance, carry its high-wear resistance, what be that 201010103651.5 " ptfe composite and products thereof preparation method " use as China Patent No. is exactly this technological line, this technique means but the one-sided wear resisting property that improves material only often, generally do not consider to keep to greatest extent the low frictional properties that polytetrafluoroethylene (PTFE) self has, self-lubricating property, be exactly due to the problem of adding material in addition, the pasty state that is not suitable for doing the PTFE thin-wall pipes is pushed application, generally can only be used for the moulding of column or bulk material, use as wear-resistant block or sealing member.
The modification technology that also has is to be applied in to add inorganic powder in PTFE resin emulsion, coating or spraying dry powder or organic materials uses as wear-resisting modification or caking agent, may have and be applied to polyamide-imide moulding resin (PAI), this pushes moulding from PTFE dispersion resin pasty state and uses different categories.
take polyamide-imide moulding resin (PAI) as main body and the patent No. is 02818667.2 " improved polyamide-imide moulding resin and preparation method thereof " its core, 57 ~ 90% polyamide-imide moulding resin (PAI) comes modification by adding a small amount of fluoropolymer and carbon fiber, improve its lubricity and wear resisting property, but the thermoplastic material that belongs to hot-melt extruded, the maintenance of its performance maximum the processing characteristics of polyamide-imide moulding resin (PAI) material own and physicals, this pushes moulding from PTFE dispersion resin pasty state and uses different categories.
The patent No. is the patent of CN200810042889.4 " abrasion-resistant fluoroplastic sleeve ", at present its technology in the car gear shifting system internal lining pipe be promoted, but due to the abrasion-proof modified dose of polyoxymethylene (POM) of wherein interpolation) material heatproof, the wearabilitys and all not ideal enough with the plyability of PTFE material such as (polyimide) PI, (polyphenylene sulfide) PPS, it need to must coordinate lubricant (estersil cream) to use when the assembling of car gear shifting system.Development along with the cable lining pipe of car gear shifting system, existing abrasion-resistant fluoroplastic sleeve technology exists some defectives also to show thereupon, general abrasion-resistant fluoroplastic sleeve, in the time of lubricant (estersil cream) loss can occurring in the car gear shifting system in special work shape environment or itself just do not add and lack under the work shape environment of lubricant (estersil cream), flexible comfortableness and the life-span of its car gear shifting system also descend thereupon.Developing a kind of new composite technology, to solve the problems referred to above imperative.
Summary of the invention
In view of this, the present invention is intended to solve in prior art, and fluoroplastics and fluoroplastic sleeve use the above technical problem that exists in the car gear shifting system.
The invention provides a kind of fluoroplastics, be prepared from by appended weight part by following material: 100 parts of polytetrafluoroethyldispersion dispersion resins; Polyamide-imide resin 3-15 part; Auxiliary agent oil 20-25 part.
Further, described ethene dispersion resin particle diameter is 400 ~ 650 μ m, apparent density 400 ~ 500g/l, squeeze RR1600=30 ~ 50MP.
Further, described ethene dispersion resin particle diameter is 400 μ m, apparent density 500g/l, squeeze RR1600=30MP.
Further, described polyamide-imide resin particle diameter≤150 μ m.
Further, described polyamide-imide resin particle diameter≤50 μ m.
Further, described auxiliary agent oil is C7 ~ 12 isoparaffin hydrocarbon polymers.
Further, described auxiliary agent oil volatilization temperature scope is 115 ~ 176 ℃;
Further, described auxiliary agent oil volatilization temperature scope is 115 ~ 139 ℃.
The present invention also provides a kind of fluoroplastic sleeve, and its above-mentioned arbitrary fluoroplastics are made, and take tetrafluoroethylene as body, polyamide-imide resin is the fluoroplastic sleeve of the specific three dimensional interpenetrating(polymer)networks composite structure of disperse phase.
In sum, fluoroplastics and fluoroplastic sleeve that formula provided by the invention is produced, its maximum is keeping low-friction coefficient and the self-lubricating property of fluoroplastics, has overcome again easy creep and the not anti abrasive defective of fluoroplastics self, has had both the optimum balance characteristic of self lubricity and wear resistance.In special work shape environment, such as in the car gear shifting system during lubricant (estersil cream) loss or itself just do not add and lack under the work shape environment of lubricant (estersil cream), it can guarantee flexible comfortableness and the Long-term Anti creep fatigue of car gear shifting system for a long time, improves work-ing life.
Embodiment
For purpose of the present invention, feature are become apparent, below in conjunction with accompanying drawing, the specific embodiment of the present invention is further described.
The fluoroplastics that one embodiment of the invention provides are prepared from by appended weight part by following material: 100 parts of polytetrafluoroethyldispersion dispersion resins (PTFE dispersion resin); Polyamide-imide resin (PAI resin) 3-15 part; Auxiliary agent oil 20-25 part.
In embodiments of the present invention, described ethene dispersion resin particle diameter is 400 ~ 650 μ m, apparent density 400 ~ 500g/l, squeeze RR1600=30 ~ 50MP.
Preferably, described ethene dispersion resin particle diameter is 400 μ m, apparent density 500g/l, squeeze RR1600=30MP.
In embodiments of the present invention, described polyamide-imide resin particle diameter≤150 μ m.
Preferably, described polyamide-imide resin particle diameter≤50 μ m.
In embodiments of the present invention, described auxiliary agent oil is C7 ~ 12 isoparaffin hydrocarbon polymers.
In embodiments of the present invention, described auxiliary agent oil volatilization temperature scope is 115 ~ 176 ℃;
Preferably, described auxiliary agent oil volatilization temperature scope is 115 ~ 139 ℃.
Utilize the above-mentioned material that the embodiment of the present invention provides to select and proportioning, just can pass through the sinter molding process, the PAI resin melting is interted in the PTFE bulk material, form irregular three-dimensional interpenetrating polymer network structure.This fluoroplastics material has had both the optimum balance characteristic of self lubricity and wear resistance.
The present invention also provides a kind of fluoroplastic sleeve, and its above-mentioned arbitrary fluoroplastics are made, and take tetrafluoroethylene as body, polyamide-imide resin is the fluoroplastic sleeve of the specific three dimensional interpenetrating(polymer)networks composite structure of disperse phase.
In order better to set forth the present invention, see also Fig. 1, please be depicted as the manufacture method schema of the fluoroplastic sleeve that one embodiment of the invention provides.
This manufacture method comprises the following steps:
S110 mixes the polytetrafluoroethyldispersion dispersion resin of 100 parts, the polyamide-imide resin of 3-15 part and the auxiliary agent oil of 20-25 part by weight;
S120 carries out ripening with above-mentioned mixed material;
The material that S130 is good with ageing takes out, and carries out pre-formed;
S140 pushes moulding to pre-formed good material;
S150 will push the processing of volatilizing of tubing after moulding, remove auxiliary agent oil, with the tubing sinter molding.
Specifically details are as follows:
One. material is prepared and pre-treatment
1. polytetrafluoroethyldispersion dispersion resin (PTFE dispersion resin), it is 400 ~ 650 μ m that described fluoroplastics are selected polytetrafluoroethyldispersion dispersion resin (PTFE dispersion resin) particle diameter, apparent density 400 ~ 500g/l, squeeze RR1600=30 ~ 50MP(ASTM D4895); PTFE dispersion resin more preferably particle diameter is=400 μ m, apparent density 500g/l, squeeze RR1600=30MP(ASTM D4895).This resin must leave in encloses container, is positioned over 0 ~ 5 ℃ of refrigerator freezing after 24 hours, sieves in≤15 ℃ of environment and removes aggregate, and screen sizes is 8 ~ 10 orders, the resin that is sieved leaves in≤15 ℃ of environment in, stand-by.
2. polyamide-imide resin (PAI resin), described polyamide-imide resin (PAI resin) maximum particle diameter≤150 μ m; PAI resin maximum particle diameter more preferably≤50 μ m.After dry 12 hours, put into moisture eliminator in 120 ~ 160 ℃ of baking ovens, leave in≤15 ℃ of environment in, stand-by.
3. auxiliary agent is oily, and described auxiliary agent oil is C7 ~ C12 isoparaffin hydrocarbon polymer, and the volatilization temperature scope is 115 ℃ ~ 176 ℃; Auxiliary agent oil is C7 ~ C9 isoparaffin hydrocarbon polymer more preferably, and volatilization temperature is 115 ~ 139 ℃.Above-mentioned auxiliary agent oil leaves in≤15 ℃ of environment in, stand-by.
Two. batching and mixing
select in an embodiment of the present invention formula 1: the above-mentioned polytetrafluoroethyldispersion dispersion resin of handling well (PTFE dispersion resin) is taken 5Kg, the polyamide-imide resin of handling well in above-mentioned 2 (PAI resin) takes 250g, put into successively mixing bottle, build lid and guarantee sealing, the mixing bottle that above-mentioned material is housed be placed on dedicated mixer mix approximately 15 ~ 20 minutes after, uncap, auxiliary agent oil in above-mentioned 3 is taken 1.15Kg, pour into uniformly and be equipped with in the material mixing bottle, again build lid and guarantee sealing, again the above-mentioned mixing bottle that material is housed is placed on and mixed on mixer approximately 15 ~ 20 minutes, above operation all must be carried out in≤15 ℃ of environment.
select formula 2 in another embodiment of the present invention: the above-mentioned polytetrafluoroethyldispersion dispersion resin of handling well (PTFE dispersion resin) is taken 5Kg, the polyamide-imide resin of handling well in above-mentioned 2 (PAI resin) takes 150g, put into successively mixing bottle, build lid and guarantee sealing, the mixing bottle that above-mentioned material is housed be placed on dedicated mixer mix approximately 15 ~ 20 minutes after, uncap, auxiliary agent oil in above-mentioned 3 is taken 1Kg, pour into uniformly and be equipped with in the material mixing bottle, again build lid and guarantee sealing, again the above-mentioned mixing bottle that material is housed is placed on and mixed on mixer approximately 15 ~ 20 minutes, above operation all must be carried out in≤15 ℃ of environment.
select formula 3 in another embodiment of the present invention: the above-mentioned polytetrafluoroethyldispersion dispersion resin of handling well (PTFE dispersion resin) is taken 5Kg, the polyamide-imide resin of handling well in above-mentioned 2 (PAI resin) takes 750g, put into successively mixing bottle, build lid and guarantee sealing, the mixing bottle that above-mentioned material is housed be placed on dedicated mixer mix approximately 15 ~ 20 minutes after, uncap, auxiliary agent oil in above-mentioned 3 is taken 1.25Kg, pour into uniformly and be equipped with in the material mixing bottle, again build lid and guarantee sealing, again the above-mentioned mixing bottle that material is housed is placed on and mixed on mixer approximately 15 ~ 20 minutes, above operation all must be carried out in≤15 ℃ of environment.
Three. ripening
The above-mentioned material that mixes connects in the environment that bottle is transferred to 30 ℃ together, carries out ripening more than 12 hours, guarantees full and uniform the swelling in the PTFE resin of auxiliary agent oil.
Four. premolding
Material that ageing is good takes out, and puts to room temperature after 30 minutes, carries out pre-formedly on the pre-formed equipment of special use, need to adjust a suitable pressure and dwell time during pre-molding, guarantees the closely knit homogeneity of material base.
Five. extrude sinter molding
In embodiments of the present invention, extrude sinter molding and can adopt horizontal mode or vertical mode.Pre-formed good material base is packed in special-purpose PTFE dispersion resin pasty state extruding machine, select suitable tube extrusion die, carry out the moulding of pushing of tubing, the tubing of pushing after moulding vapors away auxiliary agent oil by the volatilization case, enter subsequently high temperature sintering furnace and carry out final sinter molding, and obtain the described abrasion-resistant fluoroplastic sleeve of the embodiment of the present invention.
Concrete principle is as follows:
the key core technology application principle of the embodiment of the present invention, when the tubing that will push moulding according to above-mentioned manufacture method can vapor away by the most of auxiliary agent oil of volatilization case, after pushing moulding, pasty state stays the hole of some amount on raw material tubing, along with raw material tubing further enter set the high temperature sintering furnace with thermograde after, progressively vaporing away fully of auxiliary agent oil in raw material tubing, stay the hole of maximum quantity on raw material tubing, simultaneously tubing is in the increase along with the sintering oven temperature of the moving process of production line, when arriving approximately 327 ℃ (the known crystalline region fusing point of PTFE material), the PTFE body also can condense in together in melting, if be that at this moment pure PTFE resin will obtain the maximum pipe of porosity content, these hole naked eyes can not be found out, also inevitable, also one of reason of PTFE material property defective (the PTFE pasty state is pushed the known defective of sintering and moulding technology).but, polyamide-imide resin (PAI resin) has been added in the invention of this patent exactly in advance in this matrix material, the PAI resin that adds in the fluoroplastics that temperature in the time of before and after 327 ℃ (namely PTFE body melting is condensed in together the process) embodiment of the present invention provides will melt-flow be filled the full hole (this is that inorganic powder filling-modified institute is irrealizable) that stays because of the volatilization of auxiliary agent oil, utilize the above-mentioned material that the embodiment of the present invention provides to select and proportioning, just can pass through the sinter molding process, the PAI resin melting is interted in the PTFE bulk material, form irregular three-dimensional interpenetrating polymer network structure.This matrix material has had both the optimum balance characteristic of self lubricity and wear resistance.
In sum, fluoroplastics and fluoroplastic sleeve that the formula that the embodiment of the present invention provides and manufacture method are produced, its maximum is keeping low-friction coefficient and the self-lubricating property of fluoroplastics, overcome again easy creep and the not anti abrasive defective of fluoroplastics self, had both the optimum balance characteristic of self lubricity and wear resistance.In special work shape environment, such as in the car gear shifting system during lubricant (estersil cream) loss or itself just do not add and lack under the work shape environment of lubricant (estersil cream), it can guarantee flexible comfortableness and the Long-term Anti creep fatigue of car gear shifting system for a long time, improves work-ing life.
Although the present invention discloses as above with preferred embodiment; so it is not to limit the present invention; have in technical field under any and usually know the knowledgeable; without departing from the spirit and scope of the present invention; when can be used for a variety of modifications and variations, so protection scope of the present invention is as the criterion when looking claims person of defining.